The Variational Method
Introduction:
The variational method is applicable to those systems for which an approximation wave function
called the trial wave function can be guessed on the basis of their physical and chemical properties.
Explanation:
There exist systems whose Hamiltonians are known, but they cannot be solved exactly or by a
perturbative treatment. That is, there is no closely related Hamiltonian that can be solved exactly
or approximately by perturbation theory because the first order is not sufficiently accurate. One of
the approximation methods that is suitable for solving such problems is the variational method,
which is also called the Rayleigh–Ritz method. This method does not require knowledge of
simpler Hamiltonians that can be solved exactly.
Variational Method useful for:
• The variational method is useful for determining upper bound values for the eigen energies
of a system whose Hamiltonian is known. Whereas its eigenvalues and eigenstates are not
known.
• It is particularly useful for determining the ground state. It becomes quite cumbersome to
determine the energy levels of the excited states.
In the context of the variational method, one does not attempt to solve the eigenvalue problem.
but rather one uses a variational scheme to find the approximate eigen energies and eigenfunctions
from the variational equation.
where E(Ψ) is the expectation value of the energy in the state |Ψ >:
If |Ψ > depends on a parameter α E (Ψ) will also depend on α. The variational ansatz enables us to
vary α so as to minimize E (Ψ). The minimum value of E (Ψ) provides an upper limit approximation
for the true energy of the system. The variational method is particularly useful for determining
the ground state energy and its eigenstate without explicitly solving the Schrödinger equation.
Note that for any (arbitrary) trial function |Ψ > we choose, the energy E is always larger than the
exact energy E0.
the equality condition occurs only when |Ψ > is proportional to the true ground state |Ψ0 >. To
prove this, we simply expand the trial function |Ψ > in terms of the exact eigenstates of Ĥ:
With
Steps involved in variational method:
To calculate the ground state energy, we need to carry out the following four steps:
• Calculate the energy; this yields an expression which depends on the parameters α1,α2,. . :
In most cases |Ψ0 (α1,α2,…)>. will be assumed to be normalized; hence the denominator of this
expression is equal to 1.
• Third, search for the minimum of E0(α1, α2 . . .) by varying the adjustable parameters αi
until E0 is minimized. That is, minimize E(α1,α2 . .) with respect to α1,α2 . . .:
• Fourth, substitute these values of (α10, α20, . . .) to obtain the approximate value of the
energy. The value E0(α10, α20 . . .) thus obtained provides an upper bound for the exact
ground state energy E0. The exact ground state eigenstate |φ> will then be approximated
by the state |Ψ0 (α1, α2, …)>.
What about the energies of the excited states?
The variational method can also be used to find the approximate values for the energies of the first
few excited states. For instance, to find the energy and eigenstate of the first excited state that will
approximate E1 and |φ1>, we need to choose a trial function |Ψ> that must be orthogonal to |Ψ0>:
Then proceed as we did in the case of the ground state. That is, solve the variational equation for
|Ψ1>.
Similarly, to evaluate the second excited state, we solve for |Ψ2> and take into account the
following two conditions:
These conditions can be included in the variational problem by means of Lagrange multipliers,
that is, by means of a constrained variational principle. In this way, we can in principle evaluate
any other excited state. However, the variational procedure becomes increasingly complicated as
we deal with higher excited states. As a result, the method is mainly used to determine the ground
state.
